Flow batteries incorporating a nitroxide compound within an aqueous electrolyte solution

Patent metadata

Field	Value
Publication number	US-10964966-B2
Application number	US-201716469766-A
Country	US
Kind code	B2
Filing date	Dec 15, 2017
Priority date	Dec 16, 2016
Publication date	Mar 30, 2021
Grant date	Mar 30, 2021

Abstract

Flow batteries can include a first half-cell containing a first aqueous electrolyte solution, a second half-cell containing a second aqueous electrolyte solution, and a separator disposed between the first half-cell and the second half-cell. The first aqueous electrolyte solution contains a first redox-active material, and the second aqueous electrolyte solution contains a second redox-active material. At least one of the first redox-active material and the second redox-active material is a nitroxide compound or a salt thereof. Particular nitroxide compounds can include a doubly bonded oxygen contained in a ring bearing the nitroxide group, a doubly bonded oxygen appended to a ring bearing the nitroxide group, sulfate or phosphate groups appended to a ring bearing the nitroxide group, various heterocyclic rings bearing the nitroxide group, or acyclic nitroxide compounds.

First claim

What is claimed is the following:

1. A flow battery comprising:
a first half-cell containing a first aqueous electrolyte solution;
a second half-cell containing a second aqueous electrolyte solution; and
a separator disposed between the first half-cell and the second half-cell;
wherein at least one of the first redox-active material and the second redox-active material comprises a nitroxide compound having a structure of:

or a salt form thereof;
wherein:
R 1 -R 4 are, independently, optionally substituted C 1 -C 10 straight chain or branched alkyl;
each R 5 is, independently, H; optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; C 1 -C 6 polyol; C(═O)R 6 ; C(═O)OR 6 ; C(═O)NR 6 R 6 ; OR 6 ; O(C═O)R 6 ; SR 6 ; S(═O)R 6 ; S(═O) 2 R 6 ; NR 6 R 6 ; NR 6 (C═O)R 6 ; NR 6 (C═O)NR 6 R 6 ; (CH 2 ) 1-10 CO 2 H; (CH 2 ) 1-10 (CHOH)CO 2 H; CH 2 (OCH 2 CH 2 ) x OCH 3 ; CH(OH)CH 2 OH; halogen; cyano; sulfonyl; or perfluoroalkyl;
each R 6 is, independently, H; optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; perfluoroalkyl; (CH 2 ) 1-10 CO 2 H; (CH 2 ) 1-10 (CHOH)CO 2 H; (CH 2 CH 2 O) x CH 3 ; CH 2 (OCH 2 CH 2 ) x OCH 3 ; CH(OH)CH 2 OH; or C 2 -C 6 polyol;
optional double bonds are present;
a and b are, independently, 1 or 2; and
x is an integer in a range between 0 and about 100;
A 2 is C(═O)R 8 , C(═O)OR 8 , C(═O)NR 9 R 9 , NR 9 C(═O)R 9 , S(═O)OH, S(═O)R 8 , S(═O) 2 R 8 , S(═O) 2 NR 9 R 9 , OS(═O) 2 OR 10 , NR 9 C(═O)NR 9 R 9 , NR 9 C(═S)NR 9 R 9 , NR 9 S(═O) 2 R 8 , P(═O)(OR 9 ) 2 , P(═O)R 8 OR 9 , P(═O)R 8 , OP(═O)OR 10 or PR 9 ;
R 8 is optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; perfluoroalkyl; (CH 2 ) 1-10 CO 2 H; (CH 2 ) 1-10 (CHOH)CO 2 H; (CH 2 CH 2 O) x CH 3 ; CH 2 (OCH 2 CH 2 ) x OCH 3 ; CH(OH)CH 2 OH; or C 1 -C 6 polyol;
R 9 is H; optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; perfluoroalkyl; (CH 2 ) 1-10 CO 2 H; (CH 2 ) 1-10 (CHOH)CO 2 H; (CH 2 CH 2 O) x CH 3 ; CH 2 (OCH 2 CH 2 ) x OCH 3 ; CH(OH)CH 2 OH; or C 2 -C 6 polyol; and
wherein R 10 is H; optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclyl, or heteroaryl; perfluoroalkyl; (CH 2 ) 1-10 CO 2 H; (CH 2 ) 1-10 (CHOH)CO 2 H; (CH 2 CH 2 O) x CH 3 ; CH 2 (OCH 2 CH 2 ) x OCH 3 ; CH(OH)CH 2 OH; or C 2 -C 6 polyol.

2. The flow battery of claim 1 , wherein each R 5 is H, and R 1 -R 4 are each methyl.

3. The flow battery of claim 1 , wherein A 2 is S(═O)OH, S(═O)R 8 , S(═O) 2 R 8 , S(═O) 2 NR 9 R 9 , OS(═O)OR 10 , NR 9 C(═O)NR 9 R 9 , NR 9 C(═S)NR 9 R 9 , or NR 9 S(═O) 2 R 8 .

4. The flow battery of claim 3 , wherein A 2 is S(═O) 2 NR 9 R 9 or NR 9 C(═S)NR 9 R 9 , and at least one R 9 bound to N is H.

5. The flow battery of claim 3 , wherein A 2 is OS(═O)OR 10 .

6. The flow battery of claim 5 , wherein R 10 is H.

7. The flow battery of claim 1 , wherein the nitroxide compound is present in only the first aqueous electrolyte solution.

8. The flow battery of claim 7 , wherein the first aqueous electrolyte solution is a positive electrolyte solution and the first half-cell is a positive half-cell of the flow battery.

9. The flow battery of claim 8 , wherein the second half cell is a negative half-cell of the flow battery, and the second redox-active material is a coordination compound.

10. The flow battery of claim 9 , wherein the coordination compound comprises a titanium coordination compound.

11. The flow battery of claim 9 , wherein the coordination compound has a formula of:
D g M(L 1 )(L 2 )(L 3 )

wherein:
M is a transition metal or main group metal;
D is ammonium, tetraalkylammonium, an alkali metal ion, or any combination thereof;
g is an integer in a range between 0 and 6; and
L 1 , L 2 and L 3 are ligands.

12. The flow battery of claim 11 , wherein the transition metal is titanium.

13. The flow battery of claim 11 , wherein at least one of L 1 , L 2 and L 3 is a catecholate ligand or a substituted catecholate ligand.

14. The flow battery of claim 1 , wherein the salt form is an alkali metal salt form, a combination of alkali metal salt forms, an ammonium salt form, a tetraalkylammonium salt form, or any combination thereof.

15. The flow battery of claim 1 , wherein A 2 is —OS(═O) 2 OR 10 or a salt thereof.

16. The flow battery of claim 1 , wherein the nitroxide compound is [2,2,6,6,-tetramethyl-4-(sulfooxy)piperidin-1-yl]oxidanyl or a salt thereof.

17. The flow battery of claim 15 , wherein the nitroxide compound is an alkali metal, ammonium, or tetraalkylammonium salt of [2,2,6,6,-tetramethyl-4-(sulfooxy)piperidin-1-yl]oxidanyl.

Assignees

• Lockheed Martin Energy Llc

Inventors

• Norman Zachariah M
• Millard Matthew
• Nelson Emily Grace
• HUMBARGER Scott Thomas

Classifications

• C07F1/005

  without C-Metal linkages · CPC title

• H01M8/188 Primary

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• C07F3/003

  without C-Metal linkages · CPC title

• H01M4/60

  of organic compounds · CPC title

• C07D221/00

  Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 · CPC title